Method of manufacturing sputtering target and sputtering target

ABSTRACT

The manufacturing cost of a sputtering target is reduced and the impurity concentration of the manufactured sputtering target is also reduced. A method of manufacturing a sputtering target includes: surface-treating at least one of a used sputtering target and a scrap material; melting at least one of the used sputtering target and the scrap material after the surface treatment to form an ingot; and manufacturing a sputtering target by subjecting the ingot to forging, rolling, heat treating, and machining.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.15/271,911, now U.S. Pat. No. 10,533,248, filed on Sep. 21, 2016, whichis a continuation of prior International Application No.PCT/JP2015/001827 filed on Mar. 30, 2015, which is based upon and claimsthe benefit of priority from Japanese Patent Application No. 2014-073960filed on Mar. 31, 2014; the entire contents of all of which areincorporated herein by reference.

FIELD

Embodiments described herein relate generally to a method ofmanufacturing a sputtering target and a sputtering target.

BACKGROUND

In the manufacture of semiconductor components or liquid-crystalcomponents, a sputtering apparatus is used to form various kinds ofwiring and electrodes. For example, various kinds of metal thin filmsand intermetallic compound thin films are formed on a film-formationsubstrate such as a semiconductor substrate and a glass substrate by asputtering method. The aforesaid thin films are used as, for example, awiring layer, an electrode layer, a barrier layer, a foundation layer (aliner material), and the like. Impurities in the thin films have anadverse effect on operation reliability of semiconductor devices. Forthis reason, a high purity of 4 N or more is required of sputteringtargets used for forming the thin films.

Metal materials used as sputtering targets are manufactured by, forexample, a sintering method or a melting method. In the manufacture ofthe above metal materials, their raw materials are refined for reducingimpurities. An ingot is formed from the above material whose impuritiesare reduced. The ingot is worked by forging, rolling, and so on to beformed into a billet. The billet is heat-treated for its structurecontrol and so on. The billet is further shaped to a predetermined sizeby machining and the resultant billet is bonded to a cooling backingplate as required, and as a result, it is possible to manufacture thesputtering target.

As wafers and the like become larger, larger sputtering targets arerequired. In conventional methods of manufacturing sputtering targets,the increase of the target size inevitably increases manufacturing cost.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view illustrating an electron micrograph of a bondinginterface between a sputtering target and a backing plate and componentdistribution in the same.

FIG. 2 is a top view illustrating measurement positions in a surface anda thickness direction of the sputtering target.

FIG. 3 is a side view illustrating thickness-direction measurementpositions of the sputtering target.

DETAILED DESCRIPTION

A method of manufacturing a sputtering target of this embodimentincludes: surface-treating at least one of a used sputtering targetincluding a first face and a scrap material including a second face toexpose at least one of the first and second faces and remove at leastone of a part of the used sputtering target and a part of the scrapmaterial by 1 mm or more in an inward direction from the first andsecond faces, the used sputtering target and the scrap material eachcontaining a metal element, and the first and second faces each havinguniform metallic color; melting at least one of the used sputteringtarget and the scrap material after the surface treatment to form aningot; and manufacturing a sputtering target by subjecting the ingot toforging, rolling, heat treating, and machining. The sputtering targetproduced by the manufacturing method has purity equal to or higher thanthat of the used sputtering target or the scrap material.

The used sputtering target contains at least one metal element out ofTi, Zr, V, Nb, Ta, Cr, Mo, W, Co, Ir, Ni, Pd, and Pt. To fabricate theaforesaid used sputtering target a used sputtering target with adiffusion-bonded backing plate, a used sputtering target with asolder-bonded backing plate, a used sputtering integrated target withouta backing plate, or the like is used, for instance.

In the case where the used sputtering target including the backing plateis used, the backing plate is removed by, for example, cutting or heattreatment, whereby the aforesaid used sputtering target is prepared.

The scrap material contains the aforesaid metal element of the usedsputtering target. Examples of the scrap material include a scrap of aningot, a scrap of a billet, cutting chips, and other scraps from amanufacturing process of the sputtering target.

Incidentally, at least one of the used sputtering target and the scrapmaterial may be machined or cut. After it is worked into a small piecehaving a length and a width of, for example, 150 mm or less by themachining or the cutting, the small piece may be surface-treated. Thesmall piece, if having a length and a width of more than 150 mm, isdifficult to supply when it is to be melted.

In the surface treatment, surface impurities adhering to at least one ofthe surface of the used sputtering target and the surface of the scrapmaterial are removed. The surface treatment is performed using at leastone of pickling removal and mechanical removal, for instance. Thepickling removal is performed using a mixture containing two acids ormore out of hydrofluoric acid, nitric acid, hydrochloric acid, andacetic acid, for instance. Two acids or more are mixed for thetreatment, since the use of one acid has only a small effect of theimpurity removal from the surface, resulting in a long removal time.

Preferably, for example, the pickling removal is performed for a one tothirty minute cleaning time with a solution containing hydrofluoricacid, hydrochloric acid, and water whose mixture ratios are 7%, 3%, and90% respectively, or for a one to thirty minute cleaning time with asolution containing hydrofluoric acid, nitric acid, and acetic acidwhose mixture ratios are 25%, 50%, and 25% respectively. Further, inmass production, the pickling removal is preferably performed for a oneto thirty minute cleaning time with a solution containing nitric acid,hydrofluoric acid, and water whose mixture ratios are 67%, 10%, and 23%respectively. That is, the pickling removal is preferably performedusing a mixture of hydrofluoric acid having a first mixture ratio andnitric acid having a second mixture ratio higher than the first mixtureratio. The impurities can be removed even when the mixture ratios arenot as stated above, but when the contents of the acids are less thanthese ratios, the cleaning time becomes long, which is not suitable formass production.

In the surface treatment, the face having uniform metallic color in atleast one of the used sputtering target and the scrap material isexposed. Further, at least one of part of the used sputtering target andpart of the scrap material is removed by 1 mm or more in the inwarddirection from the exposed face. If the removed part is less than 1 mm,an impurity diffusion layer on the surface of, for example, the usedsputtering target cannot be sufficiently removed.

FIG. 1 is a view illustrating an electron micrograph of a bondinginterface between a sputtering target and a backing plate and componentdistribution in the same. An area where the component distribution of Tiand the component distribution of Al overlap with each other is thediffusion layer.

In the used sputtering target with the backing plate, even if thesurface appears to have uniform metallic color and thus to be made up ofa single metal when visually observed, the element (A1) forming thebacking plate material diffuses also to the Ti sputtering target side inthe bonding interface as illustrated in FIG. 1. An effective way toremove impurities including the above diffusion area is surfacetreatment to remove at least one of part of the used sputtering targetand part of the scrap material by 1 mm or more in the inward directionfrom the face having uniform metallic color.

Similarly, as for the contamination by impurities such as a surfaceoxide, the surface, even if having uniform metallic color when visuallyobserved, sometimes has a part where the impurities are diffused. In theabove case, it is preferable to remove at least one of part of the usedsputtering target and part of the scrap material by 1 mm or more in theinward direction from the face having uniform metallic color.

By removing the impurities adhering or diffused to the used sputteringtarget and the scrap material by at least one method or more out of thepickling removal and the mechanical removal, it is possible to reduce aninfluence of the contamination of the sputtering target by iron andoxygen especially when the sputtering target is used in a sputteringapparatus and an influence of the contamination of the used sputteringtarget by the backing plate (mainly an aluminum alloy).

In the step of melting at least one of the used sputtering target andthe scrap material, at least one of, for example, electron-beam melting,plasma-arc melting, and cold crucible induction melting is used to meltat least one of the used sputtering target and the scrap material. Thisfurther reduces the impurities contained in the used sputtering targetand the scrap material, making it possible for the manufacturedsputtering target to have purity equal to or higher than that of theused sputtering target.

In the electron-beam melting or the cold crucible induction melting, atleast one of the used sputtering target and the scrap material ismelted, preferably under a 1.0×10⁻¹ Pa degree of vacuum or less. Whenthe degree of vacuum is over 1.0×10⁻¹ Pa, electron beams are notsufficiently generated and moved, which is not suitable for the melting.The degree of vacuum is more preferably 6.5×10⁻³ Pa or less. If the usedsputtering target and/or the scrap material are melted under the abovedegree of vacuum, the surface thereof can be heated at high temperature,which enables degassing and refining simultaneously with the melting.Further, the above melting method uses a water-cooling copper crucibleand thus is less likely to cause a reaction with a furnace material andthe contamination by a furnace material.

In the method of manufacturing the sputtering target of this embodiment,the forging, the rolling, the heat treating, and the machining arepreferably repeated, for instance.

The purpose of the forging is to deform a cast structure of the ingothaving been melted, by the working and cause crystal grains to beoriented randomly at the time of recrystallization caused by the laterheat treatment. A reduction in area by the forging is preferably 40% ormore. When it is less than 40%, a metallic structure of the billet maynot deform sufficiently. Further, the cast structure may remain due tothe insufficient forging.

When the cast structure remains, the crystal grains are likely to beoriented in a specific direction at the time of the recrystallizationafter the heat treatment. As a result, a crystal after the heattreatment does not become fine and it may not be possible to obtain therandom orientation of the crystal grains suitable for the sputtering.

The impurities, if reduced, are not likely to hinder the movement ofgrain boundaries of the crystal grains in the heat treatment in themanufacturing process of the sputtering target. As a result, it ispossible to obtain the random orientation in the manufactured sputteringtarget.

The above-described manufacturing method can reduce the influence of thecontamination of the used sputtering target by iron and oxygen due to,for example, the sputtering apparatus or the like and the influence ofthe contamination of the used sputtering target by the backing plate(mainly consisting of an aluminum alloy or a copper alloy).

The sputtering target produced by the above-described manufacturingmethod contains the aforesaid metal element. Further, in the sputteringtarget produced by the above-described manufacturing method, oxygenamounts in the surface and the thickness direction of the sputteringtarget can be 200 ppm or less. Iron amounts in the surface and thethickness direction of the sputtering target can be 10 ppm or less.Aluminum amounts in the surface and the thickness direction of thesputtering target can be 10 ppm or less. Copper amounts in the surfaceand the thickness direction of the sputtering target can be 5 ppm orless.

The oxygen amounts in the surface and the thickness direction of thesputtering target can be within a range of +30% or less with respect toan average value of an oxygen amount in the entire sputtering target.The iron amounts in the surface and the thickness direction of thesputtering target can be within a range of +30% or less with respect toan average value of an iron amount in the entire sputtering target. Thealuminum amounts in the surface and the thickness direction of thesputtering target can be within a range of +40% or less with respect toan average value of an aluminum amount in the entire sputtering target.The copper amounts in the surface and the thickness direction of thesputtering target can be within a range of +40% or less, preferably +30%or less with respect to an average value of a copper amount in theentire sputtering target.

The oxygen amounts, the iron amounts, and the aluminum amounts in thesurface and the thickness direction of the sputtering target aremeasured as follows. FIG. 2 is a top view illustrating measurementpositions in the surface and the thickness direction of the sputteringtarget, and FIG. 3 is a side view illustrating thickness-directionmeasurement positions of the sputtering target.

As illustrated in FIG. 2, in the surface of the target in a disk shape,for example, totally 17 samples are collected at a center portion(position 1), outer periphery vicinity positions (positions 2 to 9) onfour straight lines which pass the center portion and equally divide thecircumference, and ½ distance positions (positions 10 to 17) on the fourstraight lines. Further, as illustrated in FIG. 3, in a plane (position19) at a ½ (T/2) position of the whole thickness T of the sputteringtarget, totally 17 samples are collected at the same positions(positions 1 to 17) as those in the surface (position 18). From analysisvalues of these 34 samples, the oxygen amounts, the iron amounts, andthe aluminum amounts in the surface and the thickness direction of thesputtering target are found.

For X-ray diffraction measurement in the surface and the thicknessdirection of the sputtering target, for example, 17 samples at thepositions 1 to 17 in the surface (position 18) and totally 17 samples atthe positions 1 to 17 in the plane (position 19) at the ½ (T/2) positionof the whole thickness T of the sputtering target are collected,similarly to the aforesaid analysis samples.

In X-ray diffraction patterns obtained from the X-ray diffractionmeasurement of the above 34 samples, when the combination of a firstcrystal plane having the highest peak intensity, a second crystal planehaving the second highest peak intensity, and a third crystal planehaving the third highest peak intensity are the same as the combinationof the first crystal plane, the second crystal plane, and the thirdcrystal plane in Powder Diffraction File which is data on X-raydiffraction peak intensity of powder that is an assembly of randomcrystals, it is indicated that the measured sputtering target has arandom orientation.

As described above, in this embodiment, it is possible to reduce themanufacturing cost of the sputtering target and also reduce theimpurities in the sputtering target.

Another known method to reduce the manufacturing cost of a sputteringtarget is, for example, a method of manufacturing a sputtering target bydepositing raw material powder on a substrate by a thermal sprayingmethod or the like. The use of the thermal spraying method can reducethe manufacturing cost of the sputtering target.

The manufacturing method using the thermal spraying method, however, hasnot been put into practical use as a method of manufacturing asputtering target. One reason for this is that the thermal spraying hasa difficulty in increasing the density of a deposited film. Anotherproblem is that a gas component in the target increases, since the rawmaterial powder is deposited while being melted in the atmosphere.Because of these, there occurs a serious problem that abnormal dischargeoccurs many times to increase the number of generated particles.

In a sputtering target used for forming a liquid-crystal component, inaccordance with an increase of the target size, it is required toprevent splash, which is generated due to a defect, and an increase ofparticles ascribable to the splash. In semiconductor devices, a wiringwidth is being narrowed (for example, 0.13 μm 0.09 μm and further 0.065μm or less) in order to achieve a high integration degree. Evenparticles whose diameter is as small as, for example, about 0.2 μm, ifcontaminated in the narrowed wiring and the semiconductor device havingsuch wiring, cause a wiring failure, an element failure, and so on. So,it is desired to prevent the generation of the aforesaid particles. Themethod of manufacturing the sputtering target using the thermal sprayingmethod cannot meet such a requirement at all.

On the other hand, in the manufacture of a sputtering target byrecovering and melting a used sputtering target, if the used sputteringtarget that is a high-purity sputtering target is melted, a plurality ofrefining processes can be needless. This enables a reduction in themanufacturing cost of, for example, a large-sized sputtering target. Asputtering target manufactured from a recycled used sputtering targetmay be usually lower in purity than the original used sputtering target.This is because impurities are contaminated in the step of melting theused sputtering target and the contaminated impurities cannot be removedor reduced.

The sputtering target and the method of manufacturing the sputteringtarget of this embodiment can omitt the plural refining processes. Thiscan reduce the manufacturing cost of a large-sized sputtering target.Further, by recycling a used sputtering target or a scrap materialproduced in a process of manufacturing the sputtering target, it ispossible to reduce the manufacturing cost of a large-sized target and soon. Impurities in the sputtering target can also be reduced.

The embodiments of the present invention have been presented by way ofexample only, and are not intended to limit the scope of the inventions.The novel embodiments described herein may be embodied in a variety ofother forms; furthermore, various omissions, substitutions and changesmay be made without departing from the spirit of the inventions. Theinventions described in the accompanying claims and their equivalentsare intended to cover such embodiments or modifications as would fallwithin the scope and spirit of the inventions.

EXAMPLES Example 1

From a recovered used Ti target with an Al-alloy (A6061) backing plate,the backing plate was removed by cutting. At the time of the removal ofthe backing plate, after a surface of a target material was exposed andcame to have uniform metallic color, cutting of 1 mm or more wasperformed. The targets from which the backing plate were removed and thescrap material were each cut to about 100 mm width. Their cut pieceswere pickled for ten minutes with a mixed solution of 25% hydrofluoricacid, 50% nitric acid, and 25% acetic acid, and further after thesurface came to have uniform metallic color, the cut pieces were partlyremoved by 1 mm or more by the same pickling. These materials weresubjected to electron-beam melting, and an ingot having 350 mm diameterwas fabricated. This ingot was subjected to forging with 60% reductionof area and thereafter heat-treated. Then, continually this ingot wasworked to 8 mm thickness by rolling and was primarily machined bycutting, and thereafter the target material was diffusion-bonded to anAl-alloy (A6061) backing plate. As finish machining, cutting wasperformed to fabricate a target.

Comparative Example 1

This is the used Ti target used in the example 1.

Example 2

From a recovered used Ta target with a Cu-alloy (brass) backing plate,the backing plate was removed by cutting. At the time of the removal ofthe backing plate, after a surface of a target material was exposed andcame to have uniform metallic color, cutting of 1 mm or more wasperformed. The targets from which the backing plate were removed and thescrap material were each cut to about 100 mm width. Their cut pieceswere pickled for ten minutes with a mixed solution of 67% nitric acid,10% hydrofluoric acid, and 23% water, and further after the surface cameto have uniform metallic color, the cut pieces were partly removed by 1mm or more by the same pickling. These materials were subjected toelectron-beam melting, and an ingot having 135 mm diameter wasfabricated. This ingot was subjected to forging with 45% reduction ofarea and thereafter heat-treated. Then, continually this ingot wasworked to 12 mm thickness by rolling and was primarily machined bycutting, and thereafter the target material was diffusion-bonded to aCu-alloy (brass) backing plate. As finish machining, cutting wasperformed to fabricate a target.

Comparative Example 2

This is the used Ta target used in the example 2.

Example 3

From a recovered used Ni target with an Al-alloy (A6061) backing plate,the backing plate was removed by heat treatment. The targets from whichthe backing plate were removed and the scrap material were each cut toabout 100 mm width. Their cut pieces were pickled for thirty minuteswith a mixed solution of 67% nitric acid, 10% hydrofluoric acid, and 23%water, and further after the surface came to have uniform metalliccolor, the cut pieces were partly removed by 1 mm or more by the samepickling. These materials were subjected to electron-beam melting, andan ingot having 135 mm diameter was fabricated. This ingot was subjectedto forging with 70% reduction of area and thereafter heat-treated. Then,continually this ingot was worked to 5 mm thickness by rolling and wasprimarily machined by cutting, and thereafter, the target material wasbonded to an Al-alloy (A6061) backing plate by In soldering. As finishmachining, cutting was performed to fabricate a target.

Comparative Example 3

This is the used Ni target used in the example 3.

Example 4

From the Ti target with the Al-alloy (A6061) backing plate which wasfabricated in the example 1 and was used, the backing plate was removedby cutting. At the time of the removal of the backing plate, after asurface of a target material was exposed and came to have uniformmetallic color, cutting of 1 mm or more was performed. The targets fromwhich the backing plate were removed and the scrap material were eachcut to about 100 mm width. Their cut pieces were pickled for ten minuteswith a mixed solution of 25% hydrofluoric acid, 50% nitric acid, and 25%acetic acid, and further after the surface came to have uniform metalliccolor, the cut pieces were partly removed by 1 mm or more by the samepickling. These materials were subjected to electron-beam melting, andan ingot having 350 mm diameter was fabricated. This ingot was subjectedto forging with 60% reduction of area and thereafter heat-treated. Then,continually this ingot was worked to 8 mm thickness by rolling and wasprimarily machined by cutting, and thereafter the target material wasdiffusion-bonded to an Al-alloy (A6061) backing plate. As finishmachining, cutting was performed to fabricate a target.

Example 5

From the Ti target with the Al-alloy (A6061) backing plate which wasfabricated in the example 4 and was used, the backing plate was removedby cutting. At the time of the removal of the backing plate, after asurface of a target material was exposed and came to have uniformmetallic color, cutting of 1 mm or more was performed. The targets fromwhich the backing plate were removed and the scrap material were eachcut to about 100 mm width, and their cut pieces were pickled for tenminutes with a mixed solution of 25% hydrofluoric acid, 50% nitric acid,and 25% acetic acid. These materials were subjected to electron-beammelting, and an ingot having 350 mm diameter was fabricated. This ingotwas subjected to forging with 60% reduction of area and thereafterheat-treated. Then, continually this ingot was worked to 8 mm thicknessby rolling and was primarily machined by cutting, and thereafter thetarget material was diffusion-bonded to an Al-alloy (A6061) backingplate. As finish machining, cutting was performed to fabricate a target.

Comparative Example 4

From a used Ti target with an Al-alloy (A6061) backing plate which wasthe same as that of the example 1, the backing plate was removed bycutting. At the time of the removal of the backing plate, the cuttingwas finished when the surface of a target material was exposed and cameto have uniform metallic color. The targets from which the backing platewere removed and the scrap material were each cut to about 100 mm width.Their cut pieces were subjected to electron-beam melting without beingpickled, and an ingot having 350 mm diameter was fabricated. This ingotwas subjected to forging with 60% reduction of area and thereafterheat-treated. Then, continually this ingot was worked to 8 mm thicknessby rolling and was primarily machined by cutting, and thereafter thetarget material was diffusion-bonded to an Al-alloy (A6061) backingplate. As finish machining, cutting was performed to fabricate a target.

Component analysis of iron, copper, aluminum, and oxygen was performedusing totally 34 samples collected from each of the sputtering targetsaccording to the examples 1 to 5 and the comparative examples 1 to 4 atthe aforesaid positions 1 to 17 in the surface and the plane at the ½position of the whole thickness. Tables 1 to 16 present results of theiranalysis values.

Further, X-ray diffraction measurement was conducted using totally 34samples collected from each of the sputtering targets at the aforesaidpositions 1 to 17 in the surface and the plane at the ½ position of thewhole thickness, and the order of peak intensities in major crystalplanes was investigated from obtained X-ray diffraction patterns. Tables17 and 18 present their results.

Table 1 presents iron amounts (ppm) in the surface of each of thetargets.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 4.7 0.24 1.4 5.2 4.4 5.2 0.22 1.6 9.2 2 4.4 0.28 1.64.5 5.1 4.1 0.42 1.5 8.5 3 5.3 0.25 1.3 4.8 4.7 4.8 0.47 1.3 7.5 4 4.70.26 1.3 5.9 4.5 5.8 0.28 1.4 7.1 5 5.1 0.23 1.4 5.3 5.3 6.6 0.34 1.39.7 6 4.5 0.20 1.5 5.8 4.5 5.7 0.23 1.3 11.4 7 4.1 0.26 1.4 5.9 5.1 6.50.35 1.4 6.6 8 5.5 0.19 1.6 4.7 5.3 5.6 0.27 1.5 6.7 9 5.3 0.27 1.3 4.75.8 5.5 0.34 1.4 10.8 10 5.0 0.28 1.3 4.6 5.2 5.5 0.31 1.5 7.5 11 4.90.26 1.4 4.8 5.8 6.0 0.29 1.6 11 12 4.2 0.21 1.5 4.4 4.1 6.0 0.27 1.79.2 13 4.3 0.26 1.2 3.6 5.8 5.9 0.25 1.3 11 14 3.9 0.28 1.3 4.8 4.9 5.20.31 1.3 8.9 15 4.2 0.23 1.5 4.8 4.0 4.9 0.23 1.4 8.5 16 3.9 0.27 1.65.2 4.5 5.6 0.32 1.2 13.4 17 5.1 0.24 1.3 5.5 4.7 5.8 0.41 1.4 7.4 ave.4.7 0.25 1.4 5.0 4.9 5.6 0.3 1.4 9.1

Table 2 presents a ratio (%) of a value equal to the iron amount at eachof the positions from which an overall average value of the iron amountis subtracted, to the overall average value, in the surface of thetarget.

TABLE 2 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1  1% −3%  0%  5% −11%  −7%  −30% 13%  1% 2 −5% 13%  14% −9% 4% −26%   34%  6%  −6% 3 14% 1% −8%  −3% −5%  −14%   50% −8% −17% 4 1% 5% −8%  19% −9%  4% −10% −1% −22% 5 10% −7%  0%  7% 8% 18%   9% −8% 7% 6 −3% −19%  7% 17% −9%  2% −26% −8%  26% 7 −12%  5% 0% 19% 4% 17%  12% −1% −27% 8 18% −23%  14%  −5% 8% 1% −14%  6% −26% 9 14% 9% −8%  −5%18%  −1%   9% −1%  19% 10  7% 13%  −8%  −7% 6% −1%   −1%  6% −17% 11  5%5% 0% −3% 18%  8%  −7% 13%  21% 12 −10%  −15%  7% −11%  −17%  8% −14%20%  1% 13 −8% 5% −15%  −28%  18%  6% −20% −8%  21% 14 −16%  13%  −8% −3% 0% −7%   −1% −8%  −2% 15 −10%  −7%  7% −3% −19%  −12%  −26% −1%  −6%16 −16%  9% 14%   5% −9%  1%  2% −15%   48% 17 10% −3%  −8%  11% −5%  4% 31% −1% −19%

Table 3 presents iron amounts (ppm) in the plane at the ½ thickness ofthe whole thickness direction of the target.

TABLE 3 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 4.9 0.22 1.4 5.0 3.1 6.8 0.21 1.5 8.0 2 4.2 0.3 1.4 4.73.4 4.7 0.39 1.4 6.7 3 4.5 0.27 1.3 5.5 5.4 4.4 0.43 1.2 9.4 4 5.0 0.271.5 5.7 4.7 4.9 0.34 1.3 7.7 5 5.5 0.24 1.4 5.3 4.0 5.2 0.32 1.4 7.5 65.6 0.22 1.3 4.3 4.0 5.9 0.29 1.3 10.5 7 4.1 0.24 1.2 5.7 5.2 5.4 0.321.3 7.7 8 4.4 0.2 1.5 4.0 4.7 3.7 0.3 1.5 7.2 9 5.4 0.28 1.4 5.2 4.8 6.00.29 1.3 10.3 10 4.5 0.29 1.2 5.3 4.9 5.2 0.35 1.5 8.0 11 5.5 0.27 1.45.2 4.7 5.0 0.32 1.5 7.7 12 5.9 0.23 1.3 5.3 4.8 5.0 0.30 1.6 7.2 13 5.10.29 1.3 4.2 4.8 4.4 0.26 1.3 12.3 14 5.8 0.27 1.4 3.8 4.7 4.1 0.29 1.48.3 15 6.0 0.25 1.5 3.4 5.1 5.6 0.26 1.3 8.5 16 5.6 0.29 1.4 4.2 4.8 6.60.31 1.4 13.2 17 5.3 0.26 1.5 4.9 4.5 6.7 0.36 1.6 6.9 ave. 5.1 0.26 1.44.8 4.6 5.3 0.31 1.4 8.7

Table 4 presents a ratio (%) of a value equal to the iron amount at eachof the positions from which an overall average value of the iron amountis subtracted, to the overall average value, in the plane at the ½thickness of the whole thickness direction of the target.

TABLE 4 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 −5%  −15%  2%  4% −32%  29% −33%  7%  −8% 2 −18%  16% 2% −2% −26%  −11%  24% 0% −23% 3 −12%  5% −6%  14% 18%  −17%  37% −14%  9% 4 −3%  5% 9% 19% 3% −7%  8% −7%  −11% 5 7% −7%  2% 10% −12%  −1%  2%0% −13% 6 9% −15%  −6%  −11%  −12%  12% −8% −7%   21% 7 −20%  −7%  −13% 19% 14%   2%  2% −7%  −11% 8 −14%  −23%  9% −17%  3% −30%  −4% 7% −17% 95% 8% 2%  8% 5% 14% −8% −7%   19% 10 −12%  12%  −13%  10% 7% −1% 11% 7% −8% 11 7% 5% 2%  8% 3% −5%  2% 7% −11% 12 15%  −11%  −6%  10% 5% −5%−4% 14%  −17% 13 −1%  12%  −6%  −13%  5% −17%  −17%  −7%   42% 14 13% 5% 2% −21%  3% −22%  −8% 0%  −4% 15 17%  −3%  9% −29%  12%   6% −17% −7%   −2% 16 9% 12%  2% −13%  5% 25% −1% 0%  53% 17 3% 1% 9%  2% −1% 27% 15% 14%  −20%

Table 5 presents aluminum amounts (ppm) in the surface of the target.

TABLE 5 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 0.6 0.02 0.01 1.0 1.1 1.6 0.04 0.03 9.7 2 1.1 0.04 0.020.9 1.2 1.2 0.05 0.04 10.7 3 0.8 0.04 0.02 0.6 1.2 0.8 0.06 0.02 10.6 41.1 0.03 0.02 1.0 0.8 1.0 0.02 0.03 20.2 5 1.1 0.04 0.01 0.7 0.7 0.90.03 0.04 11.5 6 1.1 0.02 0.01 0.8 0.8 1.0 0.02 0.02 11.6 7 1.3 0.020.02 1.0 1.2 0.6 0.01 0.03 10.8 8 1.2 0.03 0.01 1.1 0.9 1.4 0.05 0.0314.5 9 1.0 0.02 0.01 0.9 0.7 1.7 0.04 0.04 10.4 10 1.0 0.04 0.02 0.7 1.01.2 0.05 0.03 17.3 11 0.9 0.03 0.02 0.8 0.7 1.2 0.05 0.02 12.0 12 0.70.02 0.02 1.3 0.9 1.0 0.02 0.03 10.0 13 0.9 0.01 0.02 1.0 0.7 1.0 0.030.02 11.4 14 0.8 0.03 0.01 1.2 0.9 1.2 0.04 0.01 10.3 15 0.7 0.04 0.021.1 1.1 1.7 0.05 0.02 11.4 16 0.8 0.04 0.02 1.2 0.6 1.3 0.02 0.03 12.317 1.0 0.03 0.01 0.9 0.7 1.3 0.01 0.02 10.3 ave. 0.9 0.03 0.02 1.0 0.91.2 0.03 0.03 12.1

Table 6 presents a ratio (%) of a value equal to the aluminum amount ateach of the positions from which an overall average value of thealuminum amount is subtracted, to the overall average value, in thesurface of the target.

TABLE 6 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 −37%  −32%  −37%   5%  23%  35% 15% 11% −20% 2 16% 36%26% −6%  34%  1% 44% 48% −11% 3 −16%  36% 26% −37%   34% −32% 73% −26% −12% 4 16%  2% 26%  5% −11% −15% −42%  11%  68% 5 16% 36% −37%  −27% −22% −24% −14%  48%  −5% 6 16% −32%  −37%  −16%  −11% −15% −42%  −26%  −4% 7 37% −32%  26%  5%  34% −49% −71%  11% −10% 8 27%  2% −37%  15% 1%  18% 44% 11%  20% 9  6% −32%  −37%  −6% −22%  44% 15% 48% −14% 10 6% 36% 26% −27%   12%  1% 44% 11%  43% 11 −5%  2% 26% −16%  −22%  1%44% −26%   0% 12 −26%  −32%  26% 36%  1% −15% −42%  11% −17% 13 −5%−66%  26%  5% −22% −15% −14%  −26%   −5% 14 −16%   2% −37%  26%  1%  1%15% −63%  −15% 15 −26%  36% 26% 15%  23%  44% 44% −26%   −5% 16 −16% 36% 26% 26% −33%  10% −42%  11%  2% 17  6%  2% −37%  −6% −22%  10% −71% −26%  −15%

Table 7 presents aluminum amounts (ppm) in the plane at the ½ thicknessof the whole thickness direction of the target.

TABLE 7 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 0.9 0.02 0.02 0.8 0.9 1.7 0.04 0.03 10.1 2 0.7 0.030.02 0.8 0.8 1.2 0.06 0.04 10.9 3 1.2 0.03 0.01 1.1 0.9 1.3 0.05 0.0311.3 4 0.9 0.04 0.02 1.0 1.0 1.5 0.03 0.02 19.3 5 1.3 0.04 0.02 1.1 1.10.8 0.04 0.03 10.7 6 0.8 0.03 0.02 1.0 0.9 1.3 0.03 0.04 10.5 7 1.1 0.020.01 0.9 1.0 1.4 0.02 0.03 11.2 8 1.3 0.03 0.02 1.1 0.8 1.3 0.05 0.0213.6 9 1.0 0.02 0.02 0.7 0.9 1.5 0.03 0.03 11.4 10 1.1 0.03 0.02 0.9 0.90.9 0.04 0.03 16.8 11 1.1 0.03 0.01 1.1 0.8 1.1 0.05 0.02 11.9 12 1.00.04 0.02 1.0 0.8 0.7 0.03 0.03 9.6 13 1.0 0.03 0.02 0.9 0.8 0.8 0.020.04 10.1 14 0.9 0.04 0.02 0.9 0.9 1.0 0.04 0.02 11.5 15 1.0 0.03 0.010.8 0.9 1.6 0.05 0.02 11.0 16 0.9 0.02 0.02 0.9 0.7 1.2 0.03 0.03 10.517 0.8 0.04 0.02 0.7 0.9 1.1 0.02 0.03 10.7 ave. 1.00 0.03 0.02 0.920.88 1.20 0.04 0.03 11.83

Table 8 presents a ratio (%) of a value equal to the aluminum amount ateach of the positions from which an overall average value of thealuminum amount is subtracted, to the overall average value, in theplane at the ½ thickness of the whole thickness direction of the target.

TABLE 8 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 −10% −35%  13% −13%  2% 42%  8% 4% −15% 2 −30% −2% 13%−13%  −9%   0%  62% 39%   −8% 3  20% −2% −43%  19% 2%  8%  35% 4%  −4% 4−10% 31% 13%  8% 13%  25% −19% −31%   63% 5  30% 31% 13% 19% 25%  −33%  8% 4% −10% 6 −20% −2% 13%  8% 2%  8% −19% 39%  −11% 7  10% −35%  −43% −3% 13%  17% −46% 4%  −5% 8  30% −2% 13% 19% −9%   8%  35% −31%   15% 9 0% −35%  13% −24%  2% 25% −19% 4%  −4% 10  10% −2% 13% −3% 2% −25%   8%4%  42% 11  10% −2% −43%  19% −9%  −8%  35% −31%   1% 12  0% 31% 13%  8%−9%  −42%  −19% 4% −19% 13  0% −2% 13% −3% −9%  −33%  −46% 39%  −15% 14−10% 31% 13% −3% 2% −17%   8% −31%   −3% 15  0% −2% −43%  −13%  2% 33% 35% −31%   −7% 16 −10% −35%  13% −3% −21%   0% −19% 4% −11% 17 −20% 31%13% −24%  2% −8% −46% 4% −10%

Table 9 presents copper amounts (ppm) in the surface of the target.

TABLE 9 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 0.2 0.18 1.1 0.2 0.2 0.3 0.22 1.4 5.2 2 0.3 0.24 1.20.3 0.2 0.1 0.23 1.5 4.2 3 0.2 0.19 1.3 0.1 0.3 0.2 0.19 1.5 3.9 4 0.20.21 1.2 0.3 0.1 0.3 0.2 1.4 6.0 5 0.2 0.19 1.4 0.2 0.3 0.3 0.18 1.6 4.46 0.1 0.25 1.3 0.2 0.3 0.3 0.25 1.3 5.1 7 0.3 0.23 1.2 0.3 0.2 0.3 0.41.4 3.6 8 0.2 0.16 1.4 0.3 0.2 0.2 0.21 1.5 4.5 9 0.3 0.17 1.3 0.2 0.20.1 0.17 1.3 3.3 10 0.3 0.21 1.4 0.2 0.2 0.2 0.19 1.2 4.1 11 0.2 0.191.5 0.3 0.1 0.3 0.26 1.4 3.9 12 0.3 0.19 1.3 0.2 0.2 0.2 0.23 1.5 3.7 130.3 0.22 1.3 0.2 0.2 0.5 0.19 1.5 4.5 14 0.2 0.22 1.3 0.1 0.3 0.4 0.21.4 3.9 15 0.2 0.20 1.2 0.2 0.2 0.1 0.17 1.3 3.6 16 0.2 0.20 1.4 0.2 0.30.2 0.18 1.5 4.3 17 0.2 0.19 1.4 0.2 0.2 0.4 0.16 1.6 4.7 ave. 0.23 0.201.31 0.22 0.22 0.26 0.21 1.43 4.29

Table 10 presents a ratio (%) of a value equal to the copper amount ateach of the positions from which an overall average value of the copperamount is subtracted, to the overall average value, in the surface ofthe target.

TABLE 10 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 −13% −11%  −16%  −8% −8% 16%  3% −2% 21% 2  31% 19%−8%  38% −8% −61%   8%  5% −2% 3 −13% −6% 0% −54%  38% −23%  −11%  5%−9% 4 −13%  4% −8%  38% −54%  16%  −6% −2% 40% 5 −13% −6% 7% −8% 38% 16%−16% 12%  3% 6 −56% 24% 0% −8% 38% 16%  17% −9% 19% 7  31% 14% −8%  38%−8% 16%  87% −2% −16%  8 −13% −21%  7% 38% −8% −23%   −2%  5%  5% 9  31%−16%  0% −8% −8% −61%  −20% −9% −23%  10  31%  4% 7% −8% −8% −23%  −11%−16%  −4% 11 −13% −6% 15%  38% −54%  16%  22% −2% −9% 12  31% −6% 0% −8%−8% −23%   8%  5% −14%  13  31%  9% 0% −8% −8% 93% −11%  5%  5% 14 −13% 9% 0% −54%  38% 55%  −6% −2% −9% 15 −13% −1% −8%  −8% −8% −61%  −20%−9% −16%  16 −13% −1% 7% −8% 38% −23%  −16%  5%  0% 17 −13% −6% 7% −8%−8% 55% −25% 12% 10%

Table 11 presents copper amounts (ppm) in the plane at the ½ thicknessof the whole thickness direction of the target.

TABLE 11 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 0.3 0.22 1.2 0.2 0.3 0.2 0.19 1.4 5.4 2 0.2 0.21 1.30.2 0.2 0.1 0.2 1.4 3.8 3 0.3 0.2 1.3 0.2 0.3 0.2 0.18 1.5 3.9 4 0.20.18 1.2 0.2 0.2 0.3 0.25 1.3 6.5 5 0.3 0.18 1.4 0.2 0.2 0.3 0.23 1.55.0 6 0.2 0.21 1.3 0.2 0.3 0.2 0.23 1.4 5.3 7 0.2 0.23 1.4 0.2 0.2 0.30.35 1.4 4.0 8 0.3 0.19 1.5 0.2 0.3 0.1 0.22 1.6 4.8 9 0.2 0.2 1.2 0.20.2 0.2 0.21 1.4 4.0 10 0.2 0.18 1.3 0.2 0.2 0.4 0.18 1.4 3.9 11 0.10.21 1.4 0.2 0.1 0.1 0.24 1.3 4.1 12 0.2 0.2 1.3 0.2 0.2 0.3 0.21 1.63.9 13 0.2 0.21 1.2 0.1 0.2 0.4 0.2 1.4 5.1 14 0.3 0.23 1.4 0.2 0.3 0.40.23 1.3 4.2 15 0.2 0.19 1.2 0.2 0.2 0.3 0.2 1.6 3.9 16 0.1 0.19 1.3 0.20.2 0.3 0.18 1.5 4.1 17 0.2 0.22 1.2 0.2 0.2 0.4 0.19 1.6 5.0 ave. 0.220.20 1.30 0.19 0.22 0.26 0.22 1.45 4.52

Table 12 presents a ratio (%) of a value equal to the copper amount ateach of the positions from which an overall average value of the copperamount is subtracted, to the overall average value, in the plane at the½ thickness of the whole thickness direction of the target.

TABLE 12 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 38%  8% −8%  3%  34% −24%  −12%  −3%  19% 2 −8%  3% 0%3% −11% −62%  −8% −3% −16% 3 38% −1% 0% 3%  34% −24%  −17%   4% −14% 4−8% −11%  −8%  3% −11% 13% 15% −10%   44% 5 38% −11%  8% 3% −11% 13%  6% 4%  11% 6 −8%  3% 0% 3%  34% −24%   6% −3%  17% 7 −8% 13% 8% 3% −11%13% 61% −3% −12% 8 38% −6% 15%  3%  34% −62%   1% 11%  6% 9 −8% −1% −8% 3% −11% −24%  −3% −3% −12% 10 −8% −11%  0% 3% −11% 51% −17%  −3% −14% 11−54%   3% 8% 3% −55% −62%  11% −10%   −9% 12 −8% −1% 0% 3% −11% 13% −3%11% −14% 13 −8%  3% −8%  −48%  −11% 51% −8% −3%  13% 14 38% 13% 8% 3% 34% 51%  6% −10%   −7% 15 −8% −6% −8%  3% −11% 13% −8% 11% −14% 16−54%  −6% 0% 3% −11% 13% −17%   4%  −9% 17 −8%  8% −8%  3% −11% 51%−12%  11%  11%

Table 13 presents oxygen amounts (ppm) in the surface of the target.

TABLE 13 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 150 30 30 160 140 190 20 30 320 2 140 30 20 150 160 18030 20 300 3 150 20 20 160 150 170 30 30 350 4 140 20 30 170 160 190 2030 480 5 160 20 30 150 160 190 30 30 310 6 140 30 30 140 150 180 30 40390 7 150 30 30 170 160 170 30 30 380 8 140 30 20 160 170 180 30 30 4009 160 30 30 140 150 190 30 30 330 10 170 30 20 140 160 150 30 30 340 11130 30 20 140 140 180 20 40 380 12 170 20 30 150 170 160 30 30 310 13140 20 30 150 150 160 30 40 510 14 150 30 30 140 160 170 30 30 300 15170 20 30 160 150 170 20 30 410 16 140 20 20 170 160 170 20 30 390 17140 30 30 160 170 190 30 30 350 ave. 149.41 25.88 26.47 153.53 156.47175.88 27.06 31.18 367.65

Table 14 presents a ratio (%) of a value equal to the oxygen amount ateach of the positions from which an overall average value of the oxygenamount is subtracted, to the overall average value, in the surface ofthe target.

TABLE 14 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1  0% 16% 13%  4% −11%  8% −26%  −4% −13% 2 −6% 16% −24% −2% 2% 2% 11% −36%  −18% 3  0% −23%  −24%   4% −4%  −3%  11% −4%  −5% 4−6% −23%  13% 11% 2% 8% −26%  −4%  31% 5  7% −23%  13% −2% 2% 8% 11% −4%−16% 6 −6% 16% 13% −9% −4%  2% 11% 28%  6% 7  0% 16% 13% 11% 2% −3%  11%−4%  3% 8 −6% 16% −24%   4% 9% 2% 11% −4%  9% 9  7% 16% 13% −9% −4%  8%11% −4% −10% 10 14% 16% −24%  −9% 2% −15%  11% −4%  −8% 11 −13%  16%−24%  −9% −11%  2% −26%  28%  3% 12 14% −23%  13% −2% 9% −9%  11% −4%−16% 13 −6% −23%  13% −2% −4%  −9%  11% 28%  39% 14  0% 16% 13% −9% 2%−3%  11% −4% −18% 15 14% −23%  13%  4% −4%  −3%  −26%  −4%  12% 16 −6%−23%  −24%  11% 2% −3%  −26%  −4%  6% 17 −6% 16% 13%  4% 9% 8% 11% −4% −5%

Table 15 presents oxygen amounts (ppm) in the plane at the ½ thicknessof the whole thickness direction of the target.

TABLE 15 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 120 20 20 180 140 170 30 30 350 2 160 30 30 140 170 17030 20 330 3 120 30 20 120 160 170 30 20 320 4 130 20 30 110 170 180 2030 470 5 100 20 30 140 150 180 30 30 300 6 130 30 20 180 140 180 30 30400 7 100 30 20 170 160 160 30 20 370 8 130 30 30 160 180 180 20 20 4109 180 30 30 160 170 190 30 20 290 10 180 30 30 160 160 180 20 30 320 11120 20 30 130 170 180 30 30 400 12 170 30 30 160 150 190 30 40 330 13160 20 30 190 160 150 20 30 500 14 170 30 20 170 180 190 30 20 320 15150 30 30 160 130 170 30 20 400 16 170 20 30 160 150 180 30 30 400 17160 20 20 150 170 190 30 30 370 ave. 144.12 25.88 26.47 155.29 159.41177.06 27.65 26.47 369.41

Table 16 presents a ratio (%) of a value equal to the oxygen amount ateach of the positions from which an overall average value of the oxygenamount is subtracted, to the overall average value, in the plane at the½ thickness of the whole thickness direction of the target.

TABLE 16 Example 1 Example 2 Example 3 Example 4 Example 5 Comp. Example1 Comp. Example 2 Comp. Example 3 Comp. Example 4 Material Ti Ta Ni TiTi Ti Ta Ni Ti 1 −17%  −23%  −24%  16%  −12%  −4%  9% 13%  −5% 2 11% 16%13% −10%  7% −4%  9% −24%  −11% 3 −17%  16% −24%  −23%  0% −4%  9% −24% −13% 4 −10%  −23%  13% −29%  7% 2% −28%  13%  27% 5 −31%  −23%  13%−10%  −6%  2% 9% 13% −19% 6 −10%  16% −24%  16%  −12%  2% 9% 13%  8% 7−31%  16% −24%  9% 0% −10%  9% −24%   0% 8 −10%  16% 13% 3% 13%  2%−28%  −24%   11% 9 25% 16% 13% 3% 7% 7% 9% −24%  −21% 10 25% 16% 13% 3%0% 2% −28%  13% −13% 11 −17%  −23%  13% −16%  7% 2% 9% 13%  8% 12 18%16% 13% 3% −6%  7% 9% 51% −11% 13 11% −23%  13% 22%  0% −15%  −28%  13% 35% 14 18% 16% −24%  9% 13%  7% 9% −24%  −13% 15  4% 16% 13% 3% −18% −4%  9% −24%   8% 16 18% −23%  13% 3% −6%  2% 9% 13%  8% 17 11% −23% −24%  −3%  7% 7% 9% 13%  0%

Table 17 presents the order of the peak intensities in the major planes(first crystal plane, second crystal plane, and third crystal plane) inthe X-ray diffraction patterns of the surface of each of the targets.

TABLE 17 Example 1 Example 2 Example 3 Example 4 Example 5 Material TiTa Ni Ti Ti 1 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 2 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 3 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 4 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 5 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 6 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 7 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 8 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 9 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 10 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 11 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 12 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 13 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 14 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 15 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 16 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 17 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) Comp. Example 1 Comp. Example 2Comp. Example 3 Comp. Example 4 Material Ti Ta Ni Ti 1 (101) > (002) >(100) (110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100)2 (101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 3 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 4 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 5(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 6 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 7 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 8(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 9 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 10 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 11(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 12 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 13 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 14(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 15 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 16 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 17(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100)

Table 18 presents the order of the peak intensities in the major planes(first crystal plane, second crystal plane, and third crystal plane) inthe X-ray diffraction patterns of the plane at the ½ position of thewhole thickness of each of the targets.

TABLE 18 Example 1 Example 2 Example 3 Example 4 Example 5 Material TiTa Ni Ti Ti 1 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 2 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 3 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 4 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 5 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 6 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 7 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 8 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 9 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 10 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 11 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 12 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 13 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 14 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) 15 (101) > (002) > (100) (110) >(211) > (200) (111) > (200) > (220) (101) > (002) > (100) (101) >(002) > (100) 16 (101) > (002) > (100) (110) > (211) > (200) (111) >(200) > (220) (101) > (002) > (100) (101) > (002) > (100) 17 (101) >(002) > (100) (110) > (211) > (200) (111) > (200) > (220) (101) >(002) > (100) (101) > (002) > (100) Comp. Example 1 Comp. Example 2Comp. Example 3 Comp. Example 4 Material Ti Ta Ni Ti 1 (101) > (002) >(100) (110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100)2 (101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 3 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 4 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 5(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 6 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 7 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 8(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 9 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 10 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 11(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 12 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 13 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 14(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100) 15 (101) > (002) > (100) (110) > (211) > (200)(111) > (200) > (220) (101) > (002) > (100) 16 (101) > (002) > (100)(110) > (211) > (200) (111) > (200) > (220) (101) > (002) > (100) 17(101) > (002) > (100) (110) > (211) > (200) (111) > (200) > (220)(101) > (002) > (100)

Comparison between the example 1 and the comparative example 1, betweenthe example 2 and the comparative example 2, and between the example 3and the comparative example 3 shows that there is almost no differencein the impurity components (iron, aluminum, copper, and oxygen)therebetween. It is seen from this that purity equal to or higher thanthat of the used target can be achieved in the target fabricated throughthe melting of the used sputtering target.

Comparison between the example 1 and the comparative example 4 showsthat the values of the impurity components (iron, aluminum, copper, andoxygen) increase in the comparative example 4. It is seen from this thatpurity equal to or higher than that of the used sputtering target cannotbe achieved in the comparative example 4.

Comparison among the example 1, the example 4, and the example 5 showsthat there is no difference in the impurity components (iron, aluminum,copper, and oxygen) among them. It is seen from this that purity equalto or higher than that of the original used sputtering target can beachieved even when the target is manufactured through repeated melting.

Comparison between the examples 1 to 5 and the comparative examples 1 to4 shows that, in the targets having the same metal component, the firstcrystal plane, the second crystal plane, and the third crystal planepresent the same X-ray diffraction pattern. It is seen from this thatthe sputtering target manufactured by using the used sputtering targetalso has random orientation.

What is claimed is:
 1. A recycled sputtering target made from at leastone selected from the group consisting of a used sputtering target and ascrap material, the recycled sputtering target comprising: at least onemetal element selected from the group consisting of titanium, zirconium,vanadium, niobium, chromium, molybdenum, tungsten, cobalt, iridium,nickel, palladium and platinum; oxygen; iron; aluminum; and copper,wherein the recycled sputtering target is formed by a method comprising:surface-treating at least one selected from the group consisting of aused sputtering target including a first face and a scrap materialincluding a second face to expose at least one selected from the groupconsisting of the first and second faces and remove at least oneselected from the group consisting of a part of the used sputteringtarget and a part of the scrap material by 1 mm or more in an inwarddirection from at least one selected from the group consisting of thefirst and second faces, the used sputtering target and the scrapmaterial each containing the at least one metal element selected fromthe group consisting of titanium, zirconium, vanadium, niobium,chromium, molybdenum, tungsten, cobalt, iridium, nickel, palladium andplatinum, and the first and second faces each having uniform metalliccolor; melting the at least one selected from the group consisting ofthe used sputtering target and the scrap material after the surfacetreatment to form an ingot; and forming the recycled sputtering targetby subjecting the ingot to forging, rolling, heat treating, andmachining, wherein the at least one selected from the group consistingof the used sputtering target and the scrap material is surface-treatedby at least one selected from the group consisting of a pickling removaland a mechanical removal, the pickling removal being performed using amixture containing at least two acids selected from the group consistingof hydrofluoric acid, nitric acid, hydrochloric acid, and acetic acid,wherein the at least one selected from the group consisting of the usedsputtering target and the scrap material is melted using at least onemelting method selected from the group consisting of electron-beammelting, plasma-arc melting, and cold crucible induction melting,wherein the oxygen satisfies that oxygen amounts in a surface and athickness direction of the recycled sputtering target are within a rangeof +30% or less with respect to an average value of an oxygen amount inthe entire recycled sputtering target, wherein the iron satisfies thatiron amounts in the surface and the thickness direction of the recycledsputtering target are within a range of +30% or less with respect to anaverage value of an iron amount in the entire recycled sputteringtarget, wherein the aluminum satisfies that aluminum amounts in thesurface and the thickness direction of the recycled sputtering targetare within a range of +40% or less with respect to an average value ofan aluminum amount in the entire recycled sputtering target, wherein thecopper satisfies that copper amounts in the surface and the thicknessdirection of the recycled sputtering target are within a range of +40%or less with respect to an average value of a copper amount in theentire recycled sputtering target, wherein the oxygen satisfies thatoxygen amounts in a surface and a thickness direction of the recycledsputtering target are 200 ppm or less, wherein the iron satisfies thatiron amounts in the surface and the thickness direction of the recycledsputtering target are 10 ppm or less, wherein the aluminum satisfiesthat aluminum amounts in the surface and the thickness direction of therecycled sputtering target are 10 ppm or less, and wherein the coppersatisfies that copper amounts in the surface and the thickness directionof the recycled sputtering target are 5 ppm or less.
 2. The recycledsputtering target according to claim 1, wherein, in X-ray diffractionpatterns obtained from X-ray diffraction measurement in a surface and athickness direction of the recycled sputtering target, a combination ofa first crystal plane having the highest peak intensity, a secondcrystal plane having the second highest peak intensity, and a thirdcrystal plane having the third highest peak intensity are identical to acombination of the first crystal plane, the second crystal plane, andthe third crystal plane in data of Power Diffraction File.
 3. Therecycled sputtering target according to claim 1, wherein the picklingremoval is performed using the mixture containing the hydrofluoric acidhaving a first mixture ratio and the nitric acid having a second mixtureratio higher than the first mixture ratio.
 4. The recycled sputteringtarget according to claim 1, wherein the at least one selected from thegroup consisting of the used sputtering target and the scrap material ismelted using at least one melting method selected from the groupconsisting of the electron-beam melting and the cold crucible inductionmelting under a 1.0×10⁻¹ Pa degree of vacuum or less.
 5. The recycledsputtering target according to claim 1, comprising the titanium.
 6. Therecycled sputtering target according to claim 1, comprising the nickel.